EP0542106B1 - Procédé pour la préparation de polyisocyanates - Google Patents

Procédé pour la préparation de polyisocyanates Download PDF

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Publication number
EP0542106B1
EP0542106B1 EP92118832A EP92118832A EP0542106B1 EP 0542106 B1 EP0542106 B1 EP 0542106B1 EP 92118832 A EP92118832 A EP 92118832A EP 92118832 A EP92118832 A EP 92118832A EP 0542106 B1 EP0542106 B1 EP 0542106B1
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EP
European Patent Office
Prior art keywords
carbamic acid
acid esters
sump
distillation
bis
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Expired - Lifetime
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EP92118832A
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German (de)
English (en)
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EP0542106A3 (en
EP0542106A2 (fr
Inventor
Andreas Dr. Hauner
Hans-Joachim Dr. Hennig
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides

Definitions

  • the invention relates to a new process for the continuous production of organic polyisocyanates, in particular diisocyanates, by thermal cleavage of the carbamic acid ester on which they are based.
  • N-substituted urethanes can be split into isocyanates and alcohol [H. Ship, Ber. German Chem. Ges. 3, 649 (1870); A.W. Hoffmann, Ber. German Chem. Ges. 3, 653 (1870)].
  • EP-A-0 143 320 describes such a process at preferably high temperatures of 360-440 ° C., it being possible, if appropriate, to use comparatively low-boiling solvents whose boiling point is between those of the corresponding isocyanates and alcohols. Most likely because of the high temperature load, the yields specifically given in the examples, based on the urethane used, are clearly below 90% of theory.
  • the invention relates to a process for the continuous, catalyst-free preparation of polyisocyanates by thermal cleavage of the N-substituted carbamic acid esters corresponding to the polyisocyanates at 200 ° C. to 300 ° C.
  • a bottom-heated distillation column serving as a splitting reactor with subsequent separation of the cleavage products into a Fraction I consisting predominantly of the isocyanate component and a fraction II consisting predominantly of the alcohol component of the carbamic acid esters, the cleavage being carried out in the presence of a high boiler which is a solvent for the carbamic acid esters and is inert towards the carbamic acid esters and the cleavage products under the pressure and boiling temperature conditions in the bottom of the distillation column and having a boiling point under these pressure conditions which is at least 10 ° C above the boiling point of both cleavage products, characterized in that the car to be cleaved bamic acid esters in the form of a 5 to 90 wt .-% solution above the gap pressure to a temperature within the range of 100 ° C to 300 ° C, but a temperature which is above the melting point of the polyurethane, and then heated with relaxation are passed as a side stream into the distillation column (4), in the bottom thereof
  • the carbamic acid esters to be used in the process according to the invention are compounds of the general formula R 1 (NHCOOR 2) n .
  • R 1 represents an aliphatic hydrocarbon radical with a total of 4 to 12, in particular 5 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical with 6 to 15 carbon atoms, a xylylene radical or an aromatic hydrocarbon radical which may have methyl substituents and / or methylene bridges and has a total of 6 to 15 carbon atoms
  • R2 represents an aliphatic hydrocarbon radical having 1 to 6, in particular 1 to 4, carbon atoms, a cyclohexyl radical or a phenyl radical
  • n represents an integer from 2 to 4.
  • the polyisocyanates R 1 (NCO) n on which the carbamic acid esters are based have a boiling point under the cleavage conditions, ie under the pressure conditions in the bottom of the column (4), which is at least 10 ° C., preferably at least 40 ° C. is below or above the boiling point of the respective alcohol R2OH.
  • the polyisocyanates have a higher boiling point than the alcohols, so that the polyisocyanates are obtained as fraction I at the lower end of the dephlegmator (5).
  • the alcohol component II would of course be obtained as the lower fraction and the polyisocyanate component I as the upper fraction.
  • carbamic acid esters are 1- (butoxycarbonylamino) -3,3,5-trimethyl-5- (butoxycarbonylamino-methyl) cyclohexane 1- (methoxycarbonylamino) -3,3,5-trimethyl-5- (methoxycarbonylamino-methyl) cyclohexane 1-methyl-2,4-bis (methoxycarbonylamino) benzene 1-methyl-2,6-bis (methoxycarbonylamino) benzene 1-methyl-2,4-bis (butoxycarbonylamino) benzene 1-methyl-2,6-bis (butoxycarbonylamino) benzene 1,10-bis (methoxycarbonylamino) decane 1,12-bis (butoxycarbonylamino) dodecane 1,12-bis (methoxycarbonylamino) dodecane 1,12-bis (phenoxycarbonylamino) dodecane 1,3-bis (ethoxycarbonylamino-methyl)
  • the high boilers which can be used according to the invention are, for example, the hydrocarbons mentioned in US Pat. No. 3,919,278, column 3, lines 28 to 50, and also, for example, the various isomeric benzyltoluenes, terphenyls, phthalic acid di (ar) alkyl esters, o-phosphoric acid tri (ar) alkyl esters each having 1 to 10 carbon atoms in the (ar) alkyl radicals or any mixtures of such compounds.
  • Technical dibenzyltoluene, benzyl n-butyl phthalate or technical terphenyl are particularly preferably used.
  • the splitting columns suitable for the process according to the invention correspond to conventional distillation columns in various embodiments and can be constructed very differently.
  • the column can be filled with packing elements of the most varied types, for example Raschig rings or fabric packs made of metal or glass or can contain dividing plates, such as bubble trays, It only has to be able to be operated in such a way that the carbamic acid esters fed into the cracking column are distributed uniformly and the gaseous / liquid products / high boilers can be removed from the distillation.
  • the side stream is fed in using a suitable device, for example via a nozzle or a pressure-maintaining valve .
  • the pressure measured in the bottom of the column is 0.001 to 5 bar, preferably 10 to 500 mbar.
  • the temperature in the bottom of the column is 200 to 300 ° C. Temperature and pressure conditions are otherwise set within these ranges such that the high boilers used boil in the sump and there is a continuous depletion of carbamic acid ester in the column from the point of entry of the side stream.
  • the cleavage products are selectively condensed at the top of the column, the polyisocyanate with the higher boiling point generally being condensed in the dephlegmator (5) and collected as side stream I in (9), while the alcohol component with the lower boiling point is first condensed in the condenser (6) and as fraction II in Container (10) is collected.
  • streams I and / or II can of course be subjected to a distillative workup, in particular fraction I being freed of entrained high boilers which can be collected as a residue of the distillation and reused for the preparation of the starting solution.
  • the fractions I and II consist of at least 90% polyisocyanate R1 (NCO) n or alcohol R2OH.
  • an amount of high boilers is continuously discharged, for example via a bottom overflow, which corresponds in a first approximation to the amount of the high boilers introduced with the carbamic acid ester solution.
  • the over the swamp discharge i.e. High boilers discharged via the bottom overflow, for example collected in the bottom drain container (8), also contain small amounts of low-volatility reaction by-products, so that it is often advisable to work up the distillate before the reusable high boilers are reused.
  • An evacuated double jacket column made of glass with a diameter of 25 mm and an effective length of 400 mm serves as the gap column (4) and is filled with Raschig rings made of glass (6 x 6 mm).
  • the solution of the carbamic acid ester is fed into the lower half of the column via a heated pump (2) and a heat exchanger (3) through a pressure control valve (not shown), which is set to 5 bar.
  • the high boiler and the reaction by-products are removed by overflow of the column bottom.
  • the fission products are removed at the top of the column via two removal trays below the dephlegmator (5) and between the dephlegmator and the condenser (6).
  • the alcohols have a lower boiling point than the resulting diisocyanates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Procédé pour la préparation continue sans catalyseur de polyisocyanates par dissociation thermique des carbamates N-substitués correspondants aux polyisocyanates à une température de 200°C à 300°C dans une colonne de distillation chauffée en queue, servant de réacteur de dissociations, avec séparation subséquente des produits de la dissociation en une coupe I essentiellement constituée des constituants d'isocyanates et une coupe II essentiellement constituée des constituants d'alcools des carbamates, la dissociation étant réalisée en présence d'un constituant de point d'ébullition élevé qui est un solvant pour les carbamates, est inerte par rapport aux carbamates et aux produits de la dissociation, bout dans les conditions de pression et de température en queue de la colonne de distillation et présente dans ces conditions de pression un point d'ébullition qui se trouve au moins 10°C au-dessus du point d'ébullition des deux produits de la dissociation, caractérisé en ce qu'on chauffe les carbamates à dissocier dans la forme d'une solution de 5 à 90 % en poids au-dessus de la pression de dissociation à une température à l'intérieur du domaine de 100°C à 300°C, cependant à une température qui se trouve au-dessus du point de fusion du polyuréthane et qu'on les introduit ensuite sous décompression en tant que courant latéral dans la colonne de distillation (4), dans la queue de laquelle on maintient une pression à l'intérieur du domaine de 0,001 à 5 bars et une température à l'intérieur du domaine de 200°C à 300°C, de sorte que le constituant de point d'ébullition élevé est maintenu en ébullition en queue, simultanément les produits de la dissociation étant sélectivement condensés en continu en tête de la colonne de distillation dans la forme des coupes I et II et par l'intermédiaire de l'écoulement de queue étant extraite en continu une telle quantité du constituant de point d'ébullition élevé contenant éventuellement des impuretés qui correspond en première approximation à la quantité du constituant de point d'ébullition élevé qui est introduite dans la colonne en tant que solvant pour le carbamate.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on soumet les coupes I et II séparément à une distillation de précision, les résidus de distillation de ces distillations de précision étant renvoyés ensemble dans la colonne de distillation avec la solution de carbamate à introduire dans la colonne de distillation.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on traite par distillation l'écoulement de queue et en ce qu'on réutilise ce faisant le constituant de point d'ébullition élevé produit en tant que distillat comme solvant pour les carbamates à dissocier.
  4. Procédé selon les revendications 1 et 3, caractérisé en ce qu'on utilise en tant que carbamate au moins un composé qui correspond à la formule



            R¹ (NHCOOR²)₂



    dans laquelle
       R¹ représente le résidu d'hydrocarbure lié aux groupes isocyanates du 1,6-diisocyanatohexane, du 1-isocyanato-3,3,5-triméthyl-5-isocyanatométhylcyclohexane, du 2,4-diisocyanatotoluène, du 2,6-diisocyanatotoluène, du 2,2'-, du 2,4'- ou du 4,4'-diisocyanatodiphénylméthane, du 2,4'- ou du 4,4'-diisocyanatodicyclohexylméthane ou du 1,5-diisocyanatonaphtalène et
       R² représente un résidu alkyle avec de 1 à 4 atomes de carbone.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on utilise en tant que carbamate les bis-o-alkyluréthanes du 1,6-diisocyanatohexane, du 1-isocyanato-3,3,5-triméthyl-5-isocyanatométhylcyclohexane, du 2,4-diisocyanatotoluène ou des mélanges de ceux-ci avec du 2,6-diisocyanatotoluène présentant à chaque fois de 1 à 4 atomes de carbone dans le résidu alkyle.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on utilise en tant que constituant de point d'ébullition élevé des benzyltoluènes, des triphényles, des phtalates de di(ar)alkyles ou des o-phosphates de tri(ar)alkyles avec à chaque fois des résidus (ar)alkyles contenant de 1 à 10 atomes de carbone.
EP92118832A 1991-11-14 1992-11-03 Procédé pour la préparation de polyisocyanates Expired - Lifetime EP0542106B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4137428A DE4137428A1 (de) 1991-11-14 1991-11-14 Verfahren zur herstellung von polyisocyanaten
DE4137428 1991-11-14

Publications (3)

Publication Number Publication Date
EP0542106A2 EP0542106A2 (fr) 1993-05-19
EP0542106A3 EP0542106A3 (en) 1993-07-21
EP0542106B1 true EP0542106B1 (fr) 1995-12-27

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EP92118832A Expired - Lifetime EP0542106B1 (fr) 1991-11-14 1992-11-03 Procédé pour la préparation de polyisocyanates

Country Status (7)

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US (1) US5284969A (fr)
EP (1) EP0542106B1 (fr)
JP (1) JP3274514B2 (fr)
CA (1) CA2082786C (fr)
DE (2) DE4137428A1 (fr)
ES (1) ES2083652T3 (fr)
MX (1) MX9206304A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191179B1 (en) 1998-03-25 2001-02-20 Basf Aktiengesellschaft Preparation of polyurethane foams

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4342426A1 (de) * 1993-12-13 1995-06-14 Bayer Ag Verfahren zur Herstellung von Diurethanen und ihre Verwendung zur Herstellung von Diisocyanaten
ES2166923T3 (es) * 1996-03-15 2002-05-01 Bayer Ag Procedimiento para la disociacion termica de esteres de acidos carbamicos.
DE19907648A1 (de) * 1999-02-23 2000-08-24 Basf Ag Verfahren zur Herstellung von Isocyanaten durch Spaltung von Urethanen
EP1259480B1 (fr) 2000-02-29 2005-10-05 Huntsman International Llc Procede de preparation de polyisocyanates organiques
DE10111645A1 (de) * 2001-03-10 2002-09-19 Basf Ag Verfahren zur Herstellung von organischen Polyisocyanaten
EP2011782A1 (fr) * 2007-07-02 2009-01-07 Huntsman International Llc Procédé de synthèse de carbamates utilisant du CO2
CN101531619B (zh) * 2009-04-21 2013-04-03 山东润兴化工科技有限公司 一种氨基烷酸酯热解制备异氰酸酯的装置
CN101870665B (zh) * 2010-05-18 2014-04-30 中国科学院过程工程研究所 用于氨基甲酸酯热解反应的气液固三相逆流反应装置及其方法
JP5612115B2 (ja) 2010-10-04 2014-10-22 旭化成ケミカルズ株式会社 分離方法及びイソシアネートの製造方法
JP6022039B2 (ja) * 2013-04-03 2016-11-09 三井化学株式会社 キシリレンジイソシアネートの製造方法およびキシリレンジイソシアネートの製造装置
JP2019199427A (ja) * 2018-05-15 2019-11-21 旭化成株式会社 イソシアネートの製造方法
JPWO2023080257A1 (fr) 2021-11-08 2023-05-11

Family Cites Families (14)

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US2409712A (en) * 1944-02-03 1946-10-22 Du Pont Chemical process and products
US3870739A (en) * 1973-03-05 1975-03-11 Air Prod & Chem Isocyanates from urethanes
US3962302A (en) * 1974-03-08 1976-06-08 Atlantic Richfield Company Production of isocyanates from esters of carbamic acids (urethanes)
US3919278A (en) * 1974-06-13 1975-11-11 Atlantic Richfield Co Production of isocyanates from lower alkyl esters of mononuclear aromatic carbamic acids
US3919279A (en) * 1974-06-26 1975-11-11 Atlantic Richfield Co Catalytic production of isocyanates from esters of carbamic acids
US3919280A (en) * 1974-07-05 1975-11-11 Atlantic Richfield Co Recovery of solvents employed in the production of isocyanates from esters of carbamic acids
DE2512514C2 (de) * 1975-03-21 1982-12-30 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von aliphatischen Isocyanaten
JPS5219624A (en) * 1975-08-07 1977-02-15 Mitsui Toatsu Chem Inc Process for preparation of isocyanates
US3992430A (en) * 1975-09-11 1976-11-16 Chevron Research Company Process for preparing aromatic isocyanates
DE2756928A1 (de) * 1977-12-21 1979-07-05 Bayer Ag Verfahren zur kontinuierlichen herstellung von monoisocyanaten
DE2806214A1 (de) * 1978-02-14 1979-08-16 Bayer Ag Verfahren zur kontinuierlichen aufarbeitung von bei der phosgenierung von monoaminen anfallenden loesungen
DE2942543A1 (de) * 1979-10-20 1981-05-07 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von arylisocyanaten durch thermische spaltung von arylurethanen
DE3339300A1 (de) * 1983-10-29 1985-05-09 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von isocyanaten durch thermische spaltung von urethanen
DE3850647T2 (de) * 1987-01-13 1994-11-17 Daicel Chem Verfahren zur herstellung von isocyanat-verbindungen.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191179B1 (en) 1998-03-25 2001-02-20 Basf Aktiengesellschaft Preparation of polyurethane foams

Also Published As

Publication number Publication date
EP0542106A3 (en) 1993-07-21
ES2083652T3 (es) 1996-04-16
CA2082786C (fr) 2003-10-14
MX9206304A (es) 1993-05-01
EP0542106A2 (fr) 1993-05-19
DE59204836D1 (de) 1996-02-08
JPH05255227A (ja) 1993-10-05
CA2082786A1 (fr) 1993-05-15
DE4137428A1 (de) 1993-05-19
US5284969A (en) 1994-02-08
JP3274514B2 (ja) 2002-04-15

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